Azo dyes



Patented Apr. 7, 1942 so STATES PAT NT OFFICE AZO DYES Swanie S. Rossander and Chiles E. Sparks, Wilmington, Del., assignors to E. I. du Pont de Nemours & Company, Wilmington, DeL, a corporation of Delaware No Drawing. Application July 13, 1940,

Serial No. 345,304

5 Claims.

This invention relates to dyestuffs, in particular to colors substantive to cotton, regenerated cellulose, and certain other fibers and being,

in general, of brown shades.

The direct dyes are those which can be applied directly from a water bath to the fiber. In general such colors have bright shades and lm oderate light fastness, but lack fastness to washing, losing strength and imparting stains to interwoven fibers. In order to overcome this imperfection, it has become the practice to apply direct colors containing amino groups to the fiber and diazotizing and developing them thereon with a suitable coupling component. It is an object of this invention to make direct dyes which.

can be developed on the fiber with known developing agents to produce developed dyeings of good characteristics, particularly of fastness.

The objects of the invention are accomplished by a class of trisazo colors of which the first component has a benzene or naphthalene nucleus, the last component is an urea-meta-phenylenediamine, otherwise called 3:3'-diamino-sym.- diphenyl-urea, and the intermediate components are taken from a class of compounds having a benzene or naphthalene nucleus or being benzamido or naphthamido derivatives thereof. The nuclei of the several constitutents may have a variety of substituents, the more favorable of which are indicated hereinafter, but in the preferred form of the invention each dye molecule will have at least two water solubilizing groups.

Examples of the classes of compounds useful in the first position are:

in which Z is one or moreof the group hydrogen and sulfonic acid and Y is one or more of the and group hydrogen, alkyl, alkoxy and halogen. Specific mention is made of the following:

1-amino-naphthalene-6-sulfonic acid 2-amino-naphthalene-6-sulfonic acid 1-amino-naphthalene-4-sulfonic acid 2-naphthylamine-5,7-disulfonic acid l-amino-4-methyl-benzene-3sulfonic acid 1-amino2-chloro-benzene-5-sulfonic' acid 1-amino-3-chloro-6-methyl-benzene 4 sulfonic acid 2-amino-naphthalene-3,6-disulf0nic acid 1-amino-naphthalene3,8-disulfonic acid 2-amino-naphthalene-4,8-disu1fonic acid in which R is one or more of the group hydrogen, alkyl, and alkoxy, and Z is one or more of the group hydrogen and sulfonic acid. Specific mention is made of:

1-amino-naphthalene-7-sulfonic acid 1-amino-2-methoxy-5-methyl-benzene 1-amino-2,5-dimethyl-benezene 1-amino-2-methoxy-benzene 1-amino-3-methoxy-benzene 1-amino-2-methy1-benzene v 1+amino3-chloro-fi-methyl-benzene Examples of the more complex intermediate members are:

O NH: H II NO I I Y i R H II NC Y NH2 H and o H II s1 0 NHz H The significance of the symbols is as explained above. At least one sulfonic acid group or an equivalent should be present in the dye molecule in order to induce sufiicient water-solubility. Where the symbol H is shown in a formula, it is intended to indicate that that point of the ring is not substituted. The group (H) NH2 we may be introduced by coupling the diazo component to the parent arylamine coupling component, condensing the monoazo dye with mor p-nitro-benzoyl-chloride, and reducing the nitro group to amino.

The following examples illustrate but do not limit the scope of the invention:

Example I Slurry 30.3 parts of 2-amino-naphthalene-6,8- disulfonic acid with 300 parts of water. Ice the mixture to :2 C. and diazotize by adding 9.1 parts of hydrochloric acid followed, as rapidly as it is adsorbed, by 6.9 parts of sodium nitrite.

i2 C. Maintain Congo Red acidity and a slight excess nitrite for fifteen minutes.

Add to the diazo solution 11.2 parts of l-amino- B-methyl-benzene and five minutes later 27.2 parts of crystalline sodium acetate. Continue agitation 10-12 hours, allowing the temperature to rise to that of the surroundings.

Cool the combination to il C. and add 16.4 parts of hydrochloric acid quickly. Then add slowly 7.6 parts of sodium nitrite. Maintain, after the last addition of nitrite, for fifteen minutes a temperature of 23i2 C. Congo Red acidity, and a medium test for excess nitrite on pctassium iodide-starch papers.

Add 10% salt by volume to the diazo slurry, stir 15 minutes and then add rapidly 12 parts of 1-amino-3-methy1-benzene. Stir 15 minutes.

Dissolve 17 parts of sodium carbonate in parts of warm Water and add the solution to the coupling mixture over a period of one hour. Stir then 10-12 hours, maintaining litmus acidity, and allowing the temperature to rise to that of the surroundings.

Heat the charge to i1 C., add 10% salt and stir 30 minutes. If the dye is not completely out of solution as shown by a spot on filter paper, add 4 parts of hydrochloric acid-stillleaving the charge neutral to Congo Red. Filter.

Slurry the press cake with 800 parts of water and dissolve by adding 7 parts of sodium carbonate. Heat to 90 C., adjust the volume to 1320 parts and add 10 parts of nucharandfi parts of filtercel. Agitate at 90 C. for 30 minutes and filter. To the filtrate add 20% salt, stir one hour and filter.

Dissolvethe press cake in 800 parts of water and add 9.5 parts of hydrochloric acid. Cool to 20 C. and add 7.8 parts of sodium nitrite as rapidly as adsorbed. Maintain an excess nitrite for one hour with Congo Red acidity. Destroythe excess nitrite with sulfamic acid.

Dissolve 24.2 parts of 3,3'-diamino-sym.- diphenyl-urea in 100 parts of water with,'l.4 parts of hydrochloric acid. Add this solution to the above diazo slurry. Then make the charge neutral to Congo Red with 34 parts of crystalline sodium acetate and stir 10-12 hours.

Heat the charge to 0., make acid to Congo Red paper. with hydrochloric acid and filter. Mix

the press. cake with 12 parts of sodium carbonate and dry. The product is a dark, water-soluble powder represented by the formula:

CH3 CH Add ice as required to insure a temperature of oods, stirring being continued for 15 minutes.

The goods were rinsed in cold water and dried. Salt the charge 25%-on volume, stir one hour .Thedyeing was a red chocolate brown shade with and filter. I

excellent washing fastness and good discharge Slurry the press cake with 800 parts of water properties. and add sodium carbonate as required to make The dye developed on the fiber with beta-naphthe charge medium alkaline to Brilliant Yellow.

thol is represented by the formula: Heat to 85il C. and add rapidly 14.6 parts;

CH; CH; 7 NH S OaNa l Example 11 of sodium disulfide. Agitateone hour at this temperature, maintaining a strong excess di- C y t t e fi O Couplmgs. sulfide. The reduction i's'then considered to be naphthalene- 6,8-disulfonic acid l-amino-B- complete. I methyl-benze l-amino-3-methyl-benzene, then Salt 25% and stir one hour. Filter. clarify and isolate as in Example I. Subject the press cake to diazotization, couple Slurry the press cake with 800 parts oftwater, to 3,3'ediamino-sym.-diphenyl-urea, and isolate add '7 parts of sodium carbonate and heat to 85 as in the final coupling. of Example I. C. Add 6.8 parts of crystalline sodium acetate. This product is a dark, water-soluble powder. Holding the temperature at 85 0., add 26 parts of 30 Dyeings developed with beta-naphthol are brown. 4-nitro-benzoyl-chloride, as a 20% carbon tetra- The probable formula is:

SIO3H (H) Hots (3H3 JH= NH NIL I chloride solution, over a period of two hours. 0 Example III Add SOdillIIl carbonate as required to maintain .Couple diazotized 2-amino-naphthalene-6,8-

the solution at all times slightly alkaline to Brildisulfom-c acid to Lamin enzene as 'liant Yellow. Take samples and test for comin Example L condense this coupling with 'pleteness of condensation during the addition of 3 nitro benzoyl chloride and reduce as in Exam the 4-nitr0 be Y This test is made ple II. Diazotize this combination and couple in the fOIIOW manner; Make a Cooled Sample to 1-amino-3-methy1-benzene and then diazotize acid to Congo Red and add sodium nitrite until and couple, t 3,3'-

an excess remains for 10 minutes- Couple t0 as in the previous examples. Isolate as before. sodium carbonate solution of 2-D y 0- The product is a dark powder, soluble in hydroxy-naphthalene-7-sulfonic acid. Dye a water. Dyeings developed with beta-naphthol small piece of cotton with this solution. Conare yellow brown. The probable formula is:

Following are tabulated representative prod- ,sider e Condensatlon complete when the shade ucts of the invention, with the shades of the difference between the last two dyeings is slight. developed dyeingson cotton. The compositions of the products are designated by the components used. The arrows point from the diazo. components towards the coupling components.

Example; XXIV parts of the direct color of Example I were dissolved in about 250 parts of water, heat- Color of dcvelo ed Example Composition of product (betamapmhol) yeing IV 2-ami no-naphtha1ene-6,8-disulfonic acid l-amino-naphthalene 1-(4-amino-benzoyl- Red brown.

ammo-)-3-methyl-benzene 3,3-diam1no-sym.-di henyl-urea. V l-ammo-benzene-ksulionic acid l-ammomapht alene-fi-sulfonic acid l-(4-amino' Do.

benzoyl-amino)-3-methyl-benzene 3,3-diammo-sym.-di henyl-urea. VI 2amino-naphthalene-6,8-disulionic acid l-amino-3-methy1- enzene l-(4-amino-benzoyl- Do.

amino)-naphthalene-6-sulionic acid 3,3-diamino-sym.-diphenyl-uree. VII l-amino-benzeue-i-sulfonic acid 1- -a1:n ino-benzoyl-amino)-3-methyl-benzene 1-aminonaphthalene-o-sultomc acid 3,3-diammo-sym.-dlphenyl-urea. Chocolate brown. VIII 2-am1no-naphthalene-6,S-dlsuliomc acid l-(4-am1no-benzoyl-amino)-naphthalene l- Brown.

amino-S-methyl-benzene 3,3 -diammo-sym.-d phenyl-urea. IX 2-ammo-naphthalene-fifi-disullon c acid .l-ammo-2,5-dimethoxy-bcnzene l,nmino3- Blue chocolate brown.

methyl-benzene 3,8-d1am1no-sym-.d1pheny1-urea. X 2-ammo-naphthaleue4,8-d1sulionic acid amino-benzene 1-amino-3-mcthyl-bcuzene Brown.

3,3-diammo-sym.-d1pheynl-urea. XI 2-amino-naphthalene-qa-disultonic acid l-ammo-lamethyl-benzeue l-amino-na h- Blue chocolate brown.

thalene-d-sulionic acid 3,3-d1ammo-sym.-d1phenyl-urea. XII 2-amino-naphthalene-6,8-disulfonic acid l-amino-naphthalenc l-amino-naphthalcne-fi- Do.

sulionic acid 3,3-diamino-sym-.diphenyl-urea. XIH 2-amino-naphtha1ene-6,8-disulionic acid l-amino-naphthalene-o-sulfonic acid l-amino- Do.

naphthalene-fi sulionic acid 3,3-diammo-sym.-diphenyl-urea. XIV l-amino-benzene12,5-disul[onic acid -l-am1no-3'methyl-benzeue l-amino-naphthaleue-fi- Blue brown. sulfonic acid 3,3,-diamino-sy m.-dlphenyl-urea.

XV l-amino-benzene-2,5-disulfonicacid l-ammo-naphthalene l-amino-naphthalene-o-sulfonic Do.

acid. 3,3Qdiamino-sym.-diphenyl-urea. XVI l-amino-benzene-2,5-disulfonic acid 1 amino-naphthalene-o-sulfonic acid l-amino- Do.

naphthalene-fi-sulionic acid 3,3-d1ammo-sym.-d1phcnyl-urea.

Example Composition of product Developer Color XVII... l-amino-benzeue-3sulfonic acid 1"BIPiHO-DQPhPhSIBHPrGSUJfOHiU acid 1- Betamaphtholn Chocolate,

,amino-B-methyl-benzene 3, 3-diam1n0-sym.-dlphenyl-urea. XYIIL. 2-amiuo-naphthalene-6,8-d1sulionic acld ff) 2,5-dunethoxy-l-amino-benzene Phenyl-mcthyl- Brown. 3amino-l-n1ethyl-benzeue 3,3-dian1mo-sym.-diphenyl urea. pyrazolone. XIX .-.do H Mete-tpluylene Chocolate brow diamme. XX d0 Aceto-acet ani- Brown.

e. XXL... 2-amino-naphthalene6,B-disulfonic acid S-a miuo-l-methyl-benzene 3- Phenyl-methyl- Red brown.

aminod-methyl-benzene 3,3-diam1no-sym.-d1phenyl urea. Mpyrazolone. XXII... .do N eta-toluylene Brown.

diamine. XXIIL. d0 Aceo-acet-ani- Red brown,

of 2:3-hydroxy-naphthoic acid. Other known v coupling components may also be used.

The new products are of excellent washing fastness when developed on the fiber. Furthermore, their discharge is usually good. For satisfactory-use a considerable degree of water solubility is required in the new compounds before 1 development. This water solubility is secured by including in the dye molecule as substituents on the aryl nuclei certain water-solubilizing groups. Among-themore commonly usedwatersolubilizing-groups are sulfonic and-corboxyli nj,

acid groups, but others are also well known and to some extent used. All such water-solubilizing groups are included within the scope of this invention. In general, the inclusion in the molecule of two such groups produces a suificient degreeof water-solubility. The colors can be ing to 60-70 C. Sufficient hydrochloric acid was added to make the solution /2 spot on Congo Red paper, the mixture was cooled to 15 C., and sodium nitrite was added as fast as it was absorbed. 9/2 spot acidity on Congo Red paper, a temperature of 15 C., and a distinct test for ,excess nitrite on potassium iodide-starch paper were maintained .for one hour. An amount of beta-naphthol equivalent to 105% of the nitrite absorbed in the above tetrazotization was dissolved in 250 cc. water with just enough caustic soda for complete solution, .soda ash equivalent in amount to the hydrochloric acid used in the ,above ,tetrazotization was added and the whole was cooled to 05 C. The tetrazo slurry was added-to this beta-naphthol solution slowly while "maintaining good agitation, a temperature of 0-5" C. and soda ash alkalinity. After all of the tetrazo slurry had been added, stirring was continued for two hours at C. before filtering. The dry powders were dark brown in appearance.

The pigment thus prepared is represented by "the formula:

S OaNa prep.ared. apart from the fiber to form pigments .of useful properties. For example:

I OH Following this procedure with the direct color scan 3. The compounds represented by the formula:

|| *Q Q 0 11 0 S CH3 CH3 NH OCH;

OCH:

4. The compound 2-amino-naphthalene-6,8- disulfonie acid- 1 amino 2,5 dimethoxy ben- S OsNa As many apparently widely different embodiments of this invention may be made without departing from the spirit and scope thereof, it is to be understood that We do not limit ourselves to the specific embodiments thereof except as defined in the appended claims.

We claim:

1. The compounds represented by the formula: AN=NBN=NBN=N-urea-meta-phenylene-diamine in which A is the radical of a compound from the group consisting of the benzene and naphthalene series; and each B is the radical of a compound from the group consisting of the benzene and naphthalene series and the benzamido and naphthamido derivatives thereof the compounds having 2 to 4 sulfonic acid groups to insure satisfactory solubility characteristics.

2. The compound represented by the formula:

S 03H CH3 CH3 H O aS SWANIE S'. ROSS ANDER. CHILES E. SPARKS. 

